Process of forming naphthenic acid solutions



jform gels with the hydrocarbons.

United States Patent PROCESS OF FORMING NAPHTHENIC ACID SOLUTIONS Rudolf Kern, Neustadt, Hans Scheurer, Heidelberg, Hermann Zorn, Mannheim, and Eugen Kruppke, Heidelberg, Germany, assignors to Firma Rhein-Chemie G.m.b.H., Heidelberg, Germany No Drawing. Application April 3, 1953 Serial No. 346,784

Claims priority, application Germany April 12, 1952 27 Claims. (Cl. 252-37) The present invention relates to naphthenic acid solutions and processes of making the same and more particularly to liquid hydrocarbon solutions of naphthenic acid salts which are especially suitable for motor oils and lubricating oils.

Naphthenic acid salts have been utilized in mixture with organic solvents and particularly hydrocarbons in various chemical fields, especially for the manufacture of impregnating agents, pesticides, plastics, etc.

Naphthenic acid salts have also been added to motor oilsvand lubricating oils in order that the cation of the naphthenic acid salt might react with and neutralize the free sulfuric acid which is formed upon burning of the sulfur-containing oil. Mainly polyvalent metal salts of naphthenic acid were utilized for this purpose, i.e. barium and aluminum napthenate's. However, the use of these naphthenic acid salts was greatly limited and made extremely difiicult because of the physical characteristics of the same, particularly when mixed with liquid hydrocarbons.

The naphthenic acid salts are either insoluble or only difiicultly soluble in hydrocarbons, or the naphthenates The naphthenic acid salts therefore greatly increase the viscosity of the hydrocarbons to which they are added. This increase in viscosity is highly detrimental for many purposes and therefore prevents the use of the naphthenic acid salts and particularly the polyvalent metal salts of naphthenic acid for such purposes.

It has been attempted to overcome these drawbacks in the use of naphthenic acid salts by the addition thereto of many difierent substances. However until the present time none of these additions have proved suc-. cessful and the difficult solubility of the naphthenic acid salts and the high viscosities of the solutions of the naphthenic acid salts in hydrocarbons has proved to be an important problemin many industries.

It is therefore an object of the present invention to provide means for dissolving naphthenic acid salts in liquid hydrocarbons and hydrocarbon oils consisting of mixtures of hydrocarbons whereby greater quantities of the naphthenic acid salts can be dissolved in the liquid hydrocarbon without unduly increasing the viscosity of the hydrocarbon.

It is a further object of the present invention to provide for means of dissolving naphthenic acid salts in liquid hydrocarbons whereby the viscosity of the naphthenate-containing liquid hydrocarbon is much lower than the viscosity of the ordinary hydrocarbonsolutions of naphthenic acid salts containing the same amount of naphthenate and whereby the resinification products and other decomposition products of the liquid hydrocarbon oils are dissolved or dispersed in the hydrocarbon.

It is a still further object of the present invention to provide for the formation of'clear solutions of naphthenic. acid salts in liquid hydrocarbons.

bons for naphthenic acid salts, the second group of compounds increasing the eflect of the first group of compounds when utilized simultaneously therewith.

With the above objects in view, the present invention mainly comprises in a process of forming hydrocarbon and hydrocarbon oil solutions of naphthenic acid salts, the step of mixing a naphthenic acid salt with a liquid hydrocarbon and with at least one substance having the general formula: XO(R-O),,ROY, wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of the groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms.

The above group of compounds represented by the general formula XO-(R-O),,-R-OY will after "be referred for convenience as solvent A. It has been found according to the present invention that solvent A increases the solubility of the naphthenic acid salts in the liquid hydrocarbons either by serving as. intermediate'solvent therefor or by some unknown action. The manner in which the solvent A works is unimportant, the present invention not being limited to any theory of operation but rather to the fact that solvent A does have the desired action.

In addition it has been found that the incorporation of a second group of substances having the general formula: RO wherein R and R are alkyl, aryl, aralkyl, alkaryl or alicyclic groups and at least one of the groups R and R" contains at least 6 carbon atoms further increases the dissolving ability of the liquid by, drocarbon forthe naphthenic acid salts. This second group of substances will hereinafter be referred to as solvent B.

It should be noted that solvent B may be utilized in addition to solvent A and not in place of solvent A. Solvent A is absolutely necessary for the suflicient improvement in the dissolution of the naphthenic acid salts in the liquid hydrocarbons. Solvent B when used in addition to solvent A provides the advantage of forming clear solutions of the naphthenic acid salts.

The term naphthenic acid salts refers to any metal salt of naphthenic acid and particularly polyvalent metal salts of naphthenic acid. Aluminum naphthenate, bari- :Itis another object of the present invention to proof 2 or 3 carbon atoms, n is a whole number between 1 and 20 and either X or Y is a hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic .or acyl radical of any number of carbon atoms and the other of the groups X and Y is an alkyl, aryl, aralkyl, alkaryl, alicyclic or acyl radi cal of at least .6 carbon atoms. 7

It is preferred that n be between 2 and.7. It is fur.- ther' preferred that the radical X or Y which must be of at least 6 carbon'atoms, be of at least 8 carbon atoms,

Patented July 21, 1959 herein} and still more preferably that it be exactly 12 carbon atoms. There is no actual maximum as to the number of carbon atoms for the groups X and Y, though as a practical matter X and/or Y should not have more than 24 carbon atoms. V

In the above given general formula for solvent A, it may be seen that the portion: O--(R-O),,R--O of the compound is symmetrical and therefore any radical which may be substituted for X may equally be substituted for Y. Thus, either or both X and/or Y may be substituted by an alkyl, aryl, aralkyl, alkaryl, alicyclic or an acyl group. Either X or Y, but not both, may be substituted by a hydrogen radical. If one of the groups X or Y is substituted by a hydrogen radical, then the other group must be substituted by an alkyl, aryl, aralkyl, alkaryl, alicyclic or an acyl radical of at least 6, preferably at least 8 and most preferably exactly 12 carbon atoms. If both groups X and Y are substituted by alkyl, aryl,'aralky1, alkaryl, alicyclic or acyl radicals, then only one of the groups must be of at least 6 carbon atoms, although both groups may be of at least 6 carbon atoms. The alkyl, aryl, aralkyl, alkaryl, alicyclic or acyl groups may be either saturated or unsaturated.

It is therefore apparent that solvent A is either an esterified or etherified polyalkylene glycol or esterified or etherified ester or ether derivative of polyalkylene glycol in which there are at least 2 and at most 21 alkylene groups and in which the polyalkylene glycol is esterifled or etherified with at least one radical having at least 6 carbon atoms. The solvent A may be a monoether, a diether, a monoester, a diester, or an ether-ester of polyalkylene glycol. Preferably the solvent A will contain five alkylene groups and the alkyl, aryl, aralkyl, alkaryl, alicyclic or acyl group will contain 12 carbon atoms.

y The following are examples of different compounds which may be utilized as solvent A according to the present invention. It is to be understood that these examples are given for illustrative purposes only and the scope of the present invention is in no way meant to be limited to the specific compounds mentioned.

The following are examples of monoethers of polyalkylene glycol: i

Dodecylpentaethylene glycol, octadecenyl-hexaethylene glycol,- laurylpentapropylene glycol, 2-ethylhexy1pentaethylene glycol, nonylheptaethylene glycol, phenylethylpentaethylene glycol, methyl-cyclohexyloctaethylene glycol, p-octylphenyltetrapropylene glycol, dodecylcyclohexyl-hexapropylene glycol, hexylnaphthyltetraethylene glycol and hexylnaphthyltetrapropylene glycol.

U .The, following are examples of diethers of polyalkylen glycol:

Dodecylor laurylpentaethyleneglycolmethyl ether (the term lauryl should be understood as designating the radical from fatty alcohol produced from coconut fatty acids), p octylphenyl-tetraethyleneglycolisopropylether, octydecenyl-hexaethyleneglycol-ethylhexyl ether, 2-ethylhexyl-heptaethyleneglycolbenzylether, etc. It is to be noted that any alcohol may be utilized for the esterification of the polyalkylene glycol, including alcohols obtained by the reduction of natural or synthetic fatty acids, by the carbon monoxide hydrogenization at normal or gaised pressure, by the oxo-synthesis or by parafiin oxiation.

The following are examples of mono and diesters of V polyalkylene glycol and of ethers of polyalkylene glycol:

Pentaethyleneglycol-monostearate, hexaethylene-glycolmonostearate, dodecylbenzyl pentapropyleneglycol oleate stearoyl-pentaethyleneglycol-isopropylether stearoylpentapropyleneglycol isopropylether, benzoylpentaethylene-glycol-oleate, benzoylheptaethyleneor propyleneoctylether, and benzoylpentaethyleneglycolmethylether.

The production of solutions of naphthenic acid salts in hydrocarbons according to the process of the present invention can be accomplished in various ways. The

In H.

4 method of proceeding depends upon the specific naphthenate, polyalkylene glycol derivative and the hydrocarbon oil in which the substances are mixed. It is preferable, although not necessary, to work at raised temperatures i.e. between 150 C.

The components, namely the naphthenate, polyalkylene glycol derivative and the hydrocarbon oil may be mixed together, preferably while stirring and at raised temperature, or the polyalkylene glycol derivative may be first mixed with the hydrocarbon and then the naphthenic acid salt added, or the naphthenic acid salt may be mixed with the hydrocarbon and the polyalkylene glycol derivative added, or the polyalkylene glycol derivative first mixed with the naphthenic acid salt and the thus formed solution then added to the liquid hydrocarbon.

The amount of solvent A, namely the polyalkylene glycol derivative, can be varied within very wide ranges, for example from 1% by weight of the amount of naphthenate to equal or even more than the amount of naphthenate. The specific amount depends upon the type of naphthenate as well as upon the use to which the hydrocarbon solution of the naphthenate is to be put and on the desired viscosity of the final solution. Anyone skilled in the art can by simple pretesting determine the exact amount of solvent A to be utilized for any given purpose.

The following examples are given as illustrative of the process of the present invention specifically with the use of different compounds as solvent A. It is to be understood that these examples are in no way meant to limit the scope of the present invention.

Example I -To a gel consisting of 20 parts aluminum napththenate and 80 parts of purified light petroleum is added while stirring at a temperature of 25 C., 5 parts of pentapropylene-glycoldodecylether. This causes a sudden change from gelatinous condition to a thinly liquid, easily pourable solution.

Example II The' great viscosity-lowering effect of laurylpentapropylene glycol is illustrated by mixing with mineral oils containing various naphthenic acid salts. This is shown on the following table. The various naphthenic acid salts in the amounts given in the table were each stirred with parts by weight of a mineral oil (specific gravity at 20 C.--0.882; viscosity index-89; coking number according to Conradson0.l1; and portion insoluble in gasoline0) at a temperature of 100-110 C. until a homogeneous mixture was obtained and the viscosities of these mixtures were measured at 80 C. or 50 C. as indicated. The same solutions were then mixed with the given parts by weight of laurylpentapropylene-glycolether and the viscosity of these solu- Example 111 p The visicosityflowering effect of polyalkylene glycol derivatives is also achieved. on naphthenate solutions wh ch alreadyhavewalow viscosity. A solution of 30 parts by weight calcium naphthenate in 100 parts by Example IV Mineral oil having the viscosity at 80 C. of 18.70 cst. has the viscosity thereof increased by dissolving by weight of potassium naphthenate therein, to a value at 80 C. of 29.5 cst. An addition of 20% decylpentapropyleneglycolether causes a. reduction of the viscosity at 80 C. to 21.26 cst. A methyl ether or the benzoate of the polyalkyleneglycolether mentioned above will have the same effect. I

Example V 100 parts by weight of Tetralin and 20 parts by weight of barium naphthenate result in asolution having an average viscosity at 80C. of 15.5 cst. The addition to 100 parts by Weight of this solution of 10 parts by Weight of laurylpentaethyleneglycolether results in a lowering of the viscosity at 80 C. to 1.76 cs't.

Example VI Neutral barium naphthenate from distilled naphthenic acid having an acid number, of 180 and is in the form of a brittle resin at room temperature, in gummy state at a temperature of 100 C. and has a drop-forming temperature of more than 230 C. This substance is extremely difiicult to dissolve in mineral oil and after cooling a solution of the same in mineral oil a heavy gelatin-like mass is formed. I

A fatty alcohol having ahydroxyl number of 6.8 obtained by high pressure hydrogenation of parafiin-oxi di zed fatty acid forms with 5 moles of ethylene oxide using an alkali as catalyst of the oxethylenation a waxy mass at room temperature having a drop-forming point of 38 C.

By mixing 40 parts of the brittle barium naphthenate with parts of the polyglycol ether at 100 C. while stirring, the gummy-like structure of the substance is changed and upon cooling a thread-drawing syrup is obtained which is easily soluble in hydrocarbons without the formation of any undissolved residues.

In addition to the above described polyalkylene glycol derivatives which serve as solvent A, it is desirable to add a high boiling point ether (solvent B) to the mixture to increase the dissolving ability of the hydrocarbon and to further lower the viscosity of the formed solution. The high boiling point ethers which serve as solvent B are monoethers having the general formula 'O- wherein at least one of the radicals R and R" consists of 6 or more carbon atoms. The radicals R and R" may be aliphatic, aromatic, or alicyclic and may be derived from monoor polyhydn'c alcohols. However, in the event that the radical is derived from a polyhydiic alcohol, the polyhydric alcohol must not have any ether linkages in the molecule except the single ether linkage with the other radical, namely R or R". In other words the high boiling point other must have only one ether linkage so that the same is free of polyalkylene glycol groups. Itis this lack of poly-- alkylene glycol groups of solvent B vwhich is the distinguishing feature between solvent B and solvent A. It is advantageous that the high boiling point monoether serving as solvent B be liquid at room temperature.

It has been found according to the present invention that the high boiling point ethers of solvent B seem to serve as intermediate solvent not only for the naphthenic acid salts but also for the solvent A in the hydrocarbon solvent. j p

The following are examples of high boiling point mono-ethers according to the presentinvention. It is to beunderstood that these are illustrative only of the many compounds which may be used as solvent B and the scope of the present invention is in no way limited to the specific compounds mentioned:

Di-n-hexylether, di-n-octylether, di-n-nonylether, di-2 ethylhexylether, lauryl-2-.ethylhexylether, octadecen-9- yl-l-isobutylether, dodecylphenylether, laurylcyclohexylether, octyl-B-tetralolether, nony-l-4-methyl-cyclohexyl ether, 4-octylphenyl-2-ethylhexylether, etc. Benzyl ethers or alkyl substituted benzyl ethers of the above named or other aliphatic or alicyclic' alcohols may also be used, i.e. nonylbenzylether, octadeeenyl-4-methyl benzylether, di-benzylether, tetrahydronaphthylrnethyl-- phenylor benzylether, tetrahydronaphthylmethyl-2- ethylhexylether, butandiol-(1,3)-monooctylether, butandiol-(1,4)-dibenzylether, and butandiol- (1',4)-isobutyldodecylether.

As may be seen from the above, at least one of the radicals R and R" must be of at least 6 carbon atoms. There is no actual limit to the number of carbon atoms of either or both of the radicals though as a practical matter, radicals having less than 24 carbon atoms are preferred.

Ethers from paraflin fatty alcohols or their first run: nings upon distillation as well as the oxoor naphthene alcohols are particularly suitable, i.e. paraflin fatty alkylcyclohexylether, the first running upon distillation of do decylalkylether, etc. The term first running is to be understood as meaning the first distillate of a mixture of alcohols obtained from high pressurehydrogenation of paraffin fatty acids whereby the alcohols of the mixture have a chain length of 6-9 carbon atoms.

The naphthenic acids are those obtained by raflination of mineral oils, which by high pressure reduction or by the process of Bouveault-Blanc may be transformed into the corresponding naphthene alcohol which may be easily reacted to form the ether. As examples'of ethers which may be produced by the above described methods are,

dinaphthenylether, and naphthenyl-benzyland-2- ethylhexylether.

It is possible to use either single ether or mixtures of tWo or more ethers or other solutions or mixtures of ethers in hydrocarbons and hydrocarbon oils.

The application of a high boiling point monoether, namely solvent B increases the dissolvability of the naphthenic acid salts in the hydrocarbon or'hydrocarbon oil. Whereas a mixture of a naphthenate with a solvent A at room temperature may form a waxy mass, the addition ofv 20% of a solvent B or mixture of ethers constituting the solvent B, transforms the waxy mass into a clearsolution. The resulting clear solution may be easily diluted with a liquid hydrocarbon. l

Besides acting as intermediate solvent, theethers of solvent B also have the effect of lowering the viscosity of solutions of naphthenic acid salts, solvent A and hydrocarbon.

, The amount of high boiling point monoether which may be utilized varies within very'wide limits i.e. from very small amounts to twice the amount of a naphthenate and solvent A, or even more. The amount of solvent-B is not only dependent upon the type and amount of naph thenic acid salt or mixture of naphthenic acid salt with solvent A, but also upon the degree of solubility which is desired and the desired miscibility of the naphthenic acid salt in the liquid hydrocarbon and also upon the desired viscosity of the final solution.

The production of naphthenic acid salt solutions in added thereto; and then adding the hydrocarbon oil 7 totheu add to this mixture a solvent B; and finally to add a liquid hydrocarbon to the combined mixture. It

is also'possible to first form a solution of the liquid hydro-.

Example VII This example illustrates how the addition of a solvent B forms a clear solution of a naphthenate in a solvent A. v Various naphthenates of the cations indicated in the following table were mixed with the polyalkylene glycol derivative indicated in the table in the proportion of :1 at a temperature of 40-80 C. Upon cooling a waxy mass was obtained. This mixture was then mixed in proportion of 1:1 with a solvent B ether indicated in the table. The addition of the ether to the mixture resulted in every case in the formation of a thin liquid solution which could be easily dissolved in a hydrocarbon.

Example VIII Neutral aluminum naphthenate is very poorly soluble in a hydrocarbon such as petroleum or mineral oil. By stirring for a long time at a raised temperature of 100 C. a solution is formed which is in the form of a tough gel which upon cooling becomes non-homogeneous, a portion of the petroleum or mineral oil separating therefrom. The viscosity which is very difiicult to measure with the above solution may be judged to be approximately 6000 est. at 80 C. This gel is unsuitable for all technical purposes wherein a solution of aluminum naphthenate is desired. An addition of 4% laurylpentapropyleneglycolether lowers the viscosity of the aluminum napthenate solution in the hydrocarbon from a value above 6000 to about 160 cst.

It is further preferable to first dissolve the aluminum naphthenate in a high boiling ether of solvent B. By dissolving 10 parts by weight aluminum naphthenate in 100 parts dodecyl-Z-ethylhexylether a solution having a viscosity of 1890 est. at 80 C. is obtained. The viscosity is further lowered by the addition of 4% laurylpentapropylene glycol to about 99 est. This solution is miscible in all proportions with hydrocarbons and results in the formation of thin fluid solutions.

Example IX Example X 'r Tilfi lowering of the viscosity of the mixture of 60 parts barium naphthenateand; 30 parts laurylpentaethyleneglycolether by the addition of varying amounts of laurylethylhexylether is shown in the following table:

Viscosity of Percent by weight of laurylethylhexylether added the mixt Example XI A 50% solution of barium naphthenate in a hydrocarbon such as of the spindle oil type can be formed only with very great difliculties and is unsuitable for all technical purposes. A solution of equal concentration of the naphthenate in laurylethylhexylether is comparatively easy to produce and has a viscosity of 2335 est. at 80 C. By the addition to the above of a polyalkyleneglycol derivative the viscosity is lowered. The lowering of the viscosity is dependent to some extent on the degree of polymerization of the polyalkyleneglycol derivative.- This is illustrated as follows:

Viscosity at C., est. 20% lauryl-triethyleneglycolether 11.80 20% lauryl-pentaethyleneglycolether 11.94 20% lauryl-heptaethyleneglycolether 13.38

If the viscosity lowering substance laurylhexaethylenglycolether is further etherified with ethylhexanol to laurylhexaglycolethylhexylether, the viscosity lowering remains within the same limits and the 20% addition will result in a solution having a viscosity of 13.64 est.

Any of the above solutions may be easily mixed with liquid hydrocarbons.

Example XII The addition of the naphthenic acid salts to a motor oil by, means of a solvent A with or without a solvent B improves the activity of the motor oil even at low temperatures of i.e. 40-50" C. Likewise the addition to a lubricating oil also increases the action of the lubricating oil. The amount to be added to the motor oil or lubricating oil depends upon the sulfur content of the oil, and other properties and characteristics thereof. The amount may vary within rather wide limits, though generally amounts between 05-10% by weight of the naphthenate and solvent A with or without solvent B is suitable.

The following examples are given to illustrate the use of the present invention on the formation of motor and lubricating oils of improved properties.

Example XIII A mixture is formed of:

40 parts laurylethylhexylether 15 parts of a pentaethyleneglycolether of a fatty alcohol obtained by high pressure hydrogenation of a parafinoxygenated fatty acid having a hydroxyl number of 6.6

40 parts barium naphthenate and I5 a spsth h y phsn l.

parts of this mixture is mixed with 95 parts of a basic paraffin oil having the following properties:

In a diesel motor measuring device the above motor oil mixture is found to have the following characteristics:

Oil temperature 100 C.; and testing time 120 hours with a full load. The oil utilized was Middle East diesel oil having the sulfur content of 1%.

Upon ending the test run all the piston rings were freely movable and showed no slimeor carbon deposits. The outside as well as the inside of the piston rings had a predominantly metallie appearance.

Tests as to the lubricating properties of the used oil on an Almen-Wieland machine gave a u-value between 0.2-0.1 with a possible load of 28 plates (1400 kg).

Example XIV The following mixture was tested:

65 parts laurylethylhexylether 15 parts laurylpentapropyleneglycol ether 36 parts barium naphthenate 5 parts ethylhexylphenol To a basic paraffin oil as in Example )HII was added by weight of the above mixture and the resulting mixture was tested as a motor oil. The driving distance was 6000 kilometers without any oil change, the used oil only being replaced.

Upon ending the test drive the piston rings and the oil scraper rings were freely movable and no carbon or slime deposits were found in the piston grooves. The

piston surface and cylinder walls had a true metallic appearance.

Tests'as to the lubricating properties of the used oil in the Almen-Wieland machine showed a u-value between 0.1 and 0.2 and with a possible load of 20 plates (1000 kg).

Example XV In a two stroke diesel engine the following mixture as an addition of 10% to the above lubricating oil was tested:

20 parts barium naphthenate parts calcium naphthenate 15 parts napthenealcohol-hexaethyleneglycolether 45 parts dioctyl ether 5 parts di-tertiary-butyl-p-cresol After a ten hour test run at 4500 revolutions per minute and at a water temperature of 95 C. the piston rings were freely movable and the surfaces thereof were of metallic appearance both on the inner and on the outer surface.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characeristics of the generic or specific aspects ofthis invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms in an amount sufficient to form a solution of said naphthenic acid salt, said liquid hydrocarbon and said substance.

2. A process of forming liquid hydrocarbon solutions of naphthenic acid salts, comprising the steps of mixing at a temperature of 150 C. a liquid hydrocarbon with at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 caron atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl; alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms; and adding at said temperature to the thus formed mixture a naphthenic acid salt, said substance being present in an amount suificient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said substance.

3. A process of forming liquid hydrocarbon solutions of naphthenic acid salts, comprising the steps of mixing at a temperature of 90-150 C. a naphthenic acid salt with at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, 11 is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radi cals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms; and adding at room temperature to the thus formed mixture a liquid hydrocarbon, said substance being pressent in an amount sufiicient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said substance.

4. A'process of forming liquid hydrocarbon solutions of naphthenic acid salts, comprising the steps of dissolv ing a naphthenic acid salt in at least one warm substance having the general formula:

from the class consisting of alkyl, aryl, aralkyl, alkaryl,

alicyclic and acyl radicals having at least 6 carbon atoms;

adding to the thus formed solution at least one high boiling point monoether having the general formula:

RI I O RII wherein R and R" are selected from the group consisting of'alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals and at least one of the groups R and R contains at least 7 6 carbon atoms, thereby forming a combined solution thereof; and adding -a liquid hydrocarbon to the thus formedcombined solution said substance and said high boiling point monoether being present in an amount suf ficient to form a solution of said liquid hydrocarbon,

11 said naphthenic acid salt, said substance and said high boiling point monoether, v

5. A process of forming liquid hydrocarbon and hydrocarbon oil solutions of naphthenic acid salts, comprising the steps of dissolving a naphthenic acid salt in at least one high boiling point monoether having the general formula:

wherein R' and R" are selected from the group consisting alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals and at least one of the groups R and R contains at least 6 carbon atoms; adding to the thus formed solution at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms, said substance being in an amount of 1% to equal the weight of said naphthenic acid salt, and said high boiling point monoether being in an amount up to two-times the amount of said naphthenic acid salt plus said substance, thereby forming a combined solution, of said naphthenic acid salt, said substance and said high boiling point monoether and mixing the thus-formed combined solution with a liquid hydrocarbon, thereby forming a hydrocarbon naphthenic acid salt solution the proportions of which may be varied in all proportions while still retaining a true solution.

6. As a new product, a hydrocarbon motor oil containing in solution between O.5-10% by weight of a naphthenic acid salt and at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms, said substance being present in an amount from 1% to equal the weight of said naphthenic acid salt.

7. As a new product, a hydrocarbon lubricating oil containing in solution between 05-10% by weight of a naphthenic acid salt and at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms, said substance being present in an amount-from 1% to equal the weight of said naphthenic acid salt.

8. As a new product, a hydrocarbon motor oil containing in solution between 05-10% by weight of a naphthenic acid salt, at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole num- 12 ber betweenfl and 20,and'wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class'consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms, said substance being present in an amount from 1% to equal the weight of said naphthenic acid salt and at least one high boiling point monoether having the general formula:

R O I! whereinR"and R are selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals and at least one of the groups R and R" contains at least 6 carbon atoms, said high boiling point monoether being present in an amount of 10% to up to two times the weight of said naphthenic acid salt plus said substance.

9. As a new product, a hydrocarbon lubricating oil containing in solution between 05-10% by weight of a naphthenic acid salt, at least one substance having the general formula:

XO RO) -R-OY wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen,

alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms,

said substance being present in an amount from 1% to equal the weight of said naphthenic acid salt and at least one high boiling point monoether having the general formula:

' RI O RII wherein R is analkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number ber between 1 and 20, and wherein one of the roups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms, said substancebeing present in an amount from 1% to equal the weight of said barium naphthenate.

11. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt;

and at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number ber between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms in an amount suflicient to form a solution of said naphwherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl,

alicyclic and acyl radicals having at least 8 carbon atoms in an amount sufiicient to form a solution of said naphthenic acid salt, said liquid hydrocarbon and said substance.

13. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one substance having the general formula;

alicyclic and acyl radicals having at least 8 carbon atoms in an amount sufficient to form a solution of said naphthenic acid salt, said liquid hydrocarbon and said substance.

14. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 12 carbon atoms in an amount sufiicient to form a solution of said naphthenic acid salt, said liquid hydrocarbon and said substance.

7 15. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one monoether of a radical selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals having at least 6 carbon atoms and a polyalkylene glycol having a'minimum of 2 and a maximum of 3 carbon atoms in the alkylene group-and having a maximum of 21 alkylene groups in an amount sufficient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said monoether.

16. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one diether of a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in the alkylene group and having a maximum of 21 alkylene groups, said polyalkylene glycol being etherified at both ends of the polyalkylene glycol chain with a radical selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals at least one of which has at least 6 carbon atoms in an amount suflicient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said diether.

17. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; 'a naphthenic acid salt; and at least one monoester of, an acyl radical selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals having at least 6 carbon atoms and a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in the alkylene group and having a maximum of 21 alkylene groups in an amount suflicient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said monoester.

18. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt;

and at least one diester of a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in the alkylene group and having a maximum of 21 alkylene groups, said polyalkylene glycol being esterified at both 7 ends of the polyalkylene glycol chain with acyl radicals at least one of which has at least 6 carbon atoms in an amount suflicient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said diether.

19. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one derivative of a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in the alkylene group and having a maximum of 21 alkylene groups, said polyalkylene glycol being etherified at one end of the polyalkylene glycol chain with a radical selected from the group consisting'of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals and being esterified at the other end of said polyalkylene glycol chain with an acyl radical, at least one of said acyl, aryl, aralkyl, alkaryl, alicyclic radicals having at least 6 carbon atoms in an amount suflicient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said derivative.

20. A liquidhydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one monoether of a radical selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals having at least 12 carbon atoms and a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in the alkylene group and having a maximum of 21 alkylene groups in an amount sufficient to form a solution of said liquid hydrocarbon, said naphthenic acid salt and said monoether.

21. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt of a polyvalent metal; and at least one substance having thegeneral formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms in an amount sufiicient to form a solution of said naphthenic acid salt, said liquid hydrocarbon and said substance.

22. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; at least one substance having the general formula:

consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms; and at least one high boiling point monoether having the general formula:

R! O RII wherein R and R" are selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals and at least one of the groups R and R" contains at least 6 wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, 11 is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl,

aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected'from the class' consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms in an amount of 1% to equal the weight of said naphthenic acid salt; and at least one high boiling point monoether having the general formula:

R'-O- -R" wherein R and R are selected from the group' consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radicals and at least one of the groups R and R" contains at least 6 carbon atoms in an amount of 10% to up to two times the amount of said naphthenic acid salt plus said substance.

24. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected 'from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms in an amount of 1% to equal the weight of said naphthenic acid salt; and at least one high boiling point monoether liquid at room temperature and having the general formula:

wherein R and R" are selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and alicyclic radijcals and at least one of the groups R and R" contains at least 6 carbonsatoms and wherein both alkyl groups R and R are derived from monohydric alcohols in an amount of 10% to up to two times the'amount of said naphthenic acid salt plus said substance 25. A liquid hydrocarbon solution consisting essential- 'tially of a liquid hydrocarbon; a naphthenic acid salt; and

at least one monoether of a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in ,Z16 ly of-a liquid hydrocarbon; a naphthenic acid salt; and at least one substance having the general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of 3 carbon atoms, n is a whole number between 1 and 20, and wherein one of the groups X and Y is selected from the class consisting of hydrogen, alkyl,

aryl, aralkyl, alkaryl, alicyclic and acyl radicals and the other of said groups X and Y is selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, alicyclic and acyl radicals having at least 6 carbon atoms in an amount of 1% to equal the weight of said naphthenic acid salt;

and at least one high boiling point monoether liquid at room temperature and having the general formula:

wherein R and R" are selected from the group consisting of alkyl,aryl, aralkyl, alkaryl, and alicyclic radicals and -at least one of the groups R and R contains at least 6 carbon atoms and wherein at least one of the alkyl groups R and R" is derived from monohydric alcohols in an amount of 10% to up to two times the amount of said naphthenic acid salt plus said substance.

26. A liquid hydrocarbon solution consisting essenthe alkylene group and having 5 alkylene groups, said polyalkylene glycol being etherified at one end of the polyalkylene glycol chain by an alkyl radical of 12 carbon atoms in an amount of 1% to equal the weight of 'said naphthenic acid salt, and with dodecyloctyl ether in an amount of 10% to up to two times the amount of said naphthenic acid salt plus said monoether.

27. A liquid hydrocarbon solution consisting essentially of a liquid hydrocarbon; a naphthenic acid salt; and at 'least one monoether of a polyalkylene glycol having a minimum of 2 and a maximum of 3 carbon atoms in the alkylene group and having 5 alkylene groups, said polyalkylene glycol being etherified at one end of the polyalkylene glycol chain by an alkyl radical of 12 carbon atoms in an amount of 1% to equal the weight of said naphthenic acid salt, and with dodecyl-Z-ethylhexyl ether in an amount of 10% to up to two times the amount of said naphthic acid salt plus said monoether.

References Cited in the file of this patent UNITED STATES PATENTS 1,739,686 Merrill 2 Dec. 17, 1929 2,122,940 Hodson July s, 1938 2,227,149 Murphree .0.-. Dec. 31, 1940 OTHER REFERENCES Synthetic Organic Chemicals--pub. of Carbide and Carbon Corp., N. Y., Oct. 15, 1940, page 28. 

1. A PROCESS OF FORMING LIQUID HYDROCARBON SOLUTIONS OF NAPHTHENIC ACID SALTS, COMPRISING THE STEPS OF MIXING A NAPHTHENIC ACID SALT WITH A LIQUID HYDROCARBON AT A TEMPERATURE OF 90-150* C.; AND ADDING AT SAID TEMPERATURE TO THE THUS FORMED MIXTURE AT LEAST ONE SUBTANCE HAVING THE GENERAL FORMULA:
 11. A LIQUID HYDROCARBON SOLUTION CONSISTING ESSENTIALLY OF A LIQUID HYDROCARBON; A NAPHTHENIC ACID SALT; AND AT LEAST ONE SUBSTANCE HAVING THE GENERAL FORMULA: 